Engineering Silver‐Enriched Copper Core‐Shell Electrocatalysts to Enhance the Production of Ethylene and C2+ Chemicals from Carbon Dioxide at Low Cell Potentials

Abstract Copper catalysts are widely studied for the electroreduction of carbon dioxide (CO 2 ) to value‐added hydrocarbon products. Controlling the surface composition of copper nanomaterials may provide the electronic and structural properties necessary for carbon‐carbon coupling, thus increasing the Faradaic efficiency (FE) towards ethylene and other multi‐carbon (C 2+ ) products. Synthesis and catalytic study of silver‐coated copper nanoparticles (Cu@Ag NPs) for the reduction of CO 2 are presented. Bimetallic CuAg NPs are typically difficult to produce due to the bulk immiscibility between these two metals. Slow injection of the silver precursor, concentrations of organic capping agents, and gas environment proved critical to control the size and metal distribution of the Cu@Ag NPs. The optimized Cu@Ag electrocatalyst exhibited a very low onset cell potential of −2.25 V for ethylene formation, reaching a FE towards C 2+ products (FE C2+ ) of 43% at −2.50 V, which is 1.0 V lower than a reference Cu catalyst to reach a similar FE C2+ . The high ethylene formation at low potentials is attributed to enhanced CC coupling on the Ag enriched shell of the Cu@Ag electrocatalysts. This study offers a new catalyst design towards increasing the efficiency for the electroreduction of CO 2 to value‐added chemicals.